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- W2091887897 abstract "Silber(I)-Verbindungen 2 reagieren mit dem Organorhodium-Komplex [(η5-C5Me5)Rh(μ-CO)]2 (1) unter Bildung der kovalenten AgRh2-Derivate (μ-AgX)[(η5-C5Me5)Rh(μ-CO)]2 (3a, X = Cl; 3b, X = ONO2; 3c, X = OC( = O)CH3; 3d, X = OC( = O)CF3) oder der salzartigen AgRh4-Cluster-verbindungen [(μ4-Ag){(η5-C5Me5)Rh(μ-CO)}4]+X− (4e, X = BF4; 4f, X = PF6). Produktbestimmend ist die Natur des Anions: Bei koordinationsfähigen Anionen endet die Reaktion auf der Stufe der neutralen 1:1-Addukte (Chlorid, Nitrat, Acetat, Trifluoracetat), während schlecht koordinierende Anionen wie Tetrafluoroborat oder Hexafluorophosphat die nicht faßbaren reaktionsfähigen Zwischenstufen [(μ-Ag){(η5-C5Me5)Rh(μ-CO)}2]+X− ergeben, deren sterisch exponierte Ag-Brückenliganden einer nochmaligen Addition an die RhRh-Doppelbindung von 1 zugänglich sind und so die Bildung der kationischen AgRh4-Derivate ermöglichen. Für die kovalenten AgRh2-Komplexe 3a – c sind mit Diazomethan übersichtlich verlaufende Methylen-Insertionsreaktionen charakteristisch; auf diese Weise sind die Komplexe (μ-AgCH2X)[(η5-C5Me5)-Rh(CO)]2(5a – c) erreichbar. Transition Metal Methylene Complexes, LVIII. Covalent AgRh2- and Ionic AgRh4 Cluster Compounds via Addition of Silver(I) Halides to a Rhodium-Rhodium Double Bond Silver(I) compounds 2 react quantitatively with the organorhodium complex [(η5-C5Me5)-Rh(μ-CO)]2 (1) to yield either the covalent AgRh2 derivatives of general composition (μ-AgX)[(η5-C5Me5)Rh(μ-CO)]2 (3a, X = Cl; 3b, X = ONO2; 3c, X = OC( = O)CH3; 3d, X = OC( = O)CF3) or the ionic AgRh4 cluster compounds [(μ4-Ag){(η5-C5Me5)Rh(μ-CO)}4]+X− (4e, X = BF4; 4f, X = PF6). The nature of the anion turns out to play a product-determining role. Thus, with anions that are capable of coordination, the reactions terminate at the stage of the neutral 1 : 1-adducts (chloride, nitrate, acetate, trifluoroacetate), while noncoordinating anions such as tetrafluoroborate and hexafluorophosphate first yield the reactive intermediates [(μ-Ag){(η-5-C5Me5)Rh-(μ-CO)}2]+ X−, the sterically exposed bridging silver ligand of the latter being accessible to further addition to the RhRh double bond of 1 with formation of the cationic AgRh4 derivatives. – Characteristic of the covalent AgRh2, complexes 3a – c are clean methylene insertion reactions with diazomethane that lead to compounds 5a – e of composition (μ-AgCH2X)[(η5-C5Me5)-Rh(CO)]2." @default.
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- W2091887897 date "1985-10-01" @default.
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- W2091887897 title "Übergangsmetall-Methylen-Komplexe, LVIII. Kovalente AgRh2- und ionische AgRh4-Clusterverbindungen durch Addition von Silber(I)-Salzen an eine Rhodium-Rhodium-Doppelbindung" @default.
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- W2091887897 doi "https://doi.org/10.1002/cber.19851181002" @default.
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